分子印迹整体柱在样品前处理及色谱分析中的应用

分子印迹整体柱(MIPMC)结合了分子印迹聚合物的立体选择性高和整体柱制备简单、柱压低以及传质速率快等优点,是一种极具应用潜力的样品前处理介质和色谱固定相.该文详细介绍了分子印迹整体柱的制备方法,综述了近年分子印迹整体柱在样品前处理及色谱分析中的应用进展,并对其发展趋势做了展望.     

水相识别分子印迹技术

在各种基于超分子方法的仿生识别体系中,分子印迹聚合物已经证明是一种有潜力的合成受体,受到了广泛的关注。传统的分子印迹技术通常是在有机溶剂中制备对小分子具有选择性的印迹聚合物,而在水相中制备及识别生物大分子的研究仍具有相当的挑战性。从小分子到生物大分子、从有机相到水相,反映了分子印迹技术的发展趋势。本文对最近几年分子印迹在水相制备与识别方面的最新进展进行了总结与评述,探讨了水相识别印迹聚合物的设计策略与制备方法;着重介绍了水相识别技术在固相萃取、色谱固定相、药物控释、中药有效成份提取以及生物分子识别等方面的应用;指出了提高水相识别选择性的途径并对其将来的发展进行了建议与展望。     

分子印迹电化学传感器的研究进展

本文综述了分子印迹电化学传感器的制备及其在电分析化学领域中的应用研究。引用文献83篇。     

Photo‐stimulated “turn‐on/off” molecularly imprinted polymers based on magnetic mesoporous silicon surface for efficient detection of sulfamerazine

In this study, novel photo‐stimulated molecularly imprinted polymers based on magnetic mesoporous carrier surface were developed for selective identification and intelligent separation of sulfamerazine in complex samples. The photosensitive monomer of the molecularly imprinted polymers was azobenzene derivative 5‐[(4‐(methacryloyloxy)phenyl) diazenyl] isophthalic acid with stimulus reaction mechanisms, which has photoisomerization between trans and cis for N=N bonds. Further, the properties of the photo‐stimulated molecularly imprinted polymers were further evaluated through several sets of adsorption experiments. It illustrated that the maximum adsorption amount is 0.45 mmol/L. By ultraviolet spectrophotometry, the material reaches typical characteristic peaks of photo sensitivity, and the cycle time is 16 min. Three adsorption and desorption processes were repeated, the adsorption rate reached 34.4%. Overall, the photo‐stimulated molecularly imprinted polymers can enrich and separate determine sulfamerazine with high selectivity, which have good recovery for real samples.     

Electrochemical sensing with electrodes modified with molecularly imprinted polymer films

This article summarises our work on the development of voltammetric sensors based on molecularly imprinted polymers. Several recognition elements and integration strategies were used:1.membranes electropolymerised at the electrode surface; 2.casting of polymeric membranes by drop-coating a solution of pre-formed polymer (polyphosphazene) and template in a low-boiling-point solvent on to the electrode surface; 3.preparation of composite membranes containing conductive material (graphite or carbon black), acrylic-type molecularly imprinted polymers (small particle size), and PVC as binder; and 4.in-situ polymerisation of a thin layer of acrylic imprinted polymer deposited on the electrode surface by spin coating.All the options evaluated offer the possibility of controlling electrode characteristics such as hydrophobic/hydrophilic character, permeability, or film thickness, which are essential for obtaining good sensor performance.     

利用分子印迹技术预处理生物样品中头孢药物的研究

优化了头孢硫脒分子印迹聚合物的合成条件,探讨了分子印迹技术和固相萃取联用对血浆中头孢硫脒的分离富集,发现用4-乙烯基吡啶作功能单体合成的分子印迹聚合物作为固相萃取填充料,能定量吸附血浆中的头孢硫脒,并初步研究了其吸附机理。     

Preparation and characterization of molecularly imprinted polymers based on β‐cyclodextrin‐stabilized Pickering emulsion polymerization for selective recognition of erythromycin from river water and milk

Molecularly imprinted polymers were prepared via β‐cyclodextrin‐stabilized oil‐in‐water Pickering emulsion polymerization for selective recognition and adsorption of erythromycin. The synthesized molecularly imprinted polymers were spherical in shape, with diameters ranging from 20 to 40 µm. The molecularly imprinted polymers showed high adsorption capacity (87.08 mg/g) and adsorption isotherm data fitted well with Langmuir model. Adsorption kinetics study demonstrated that the molecularly imprinted polymers acted in a fast adsorption kinetic pattern and the adsorption features of molecularly imprinted polymers followed a pseudo‐first‐order model. Adsorption selectivity analysis revealed that molecularly imprinted polymers had a much better specificity for erythromycin than that for spiramycin or amoxicillin, and the relative selectivity coefficient values on the bases of spiramycin and amoxicillin were 3.97 and 3.86, respectively. The Molecularly imprinted polymers also showed a satisfactory reusability after four times of regeneration. In addition, molecularly imprinted polymers exhibited good adsorption capacities for erythromycin under complicated environment, that is, river water and milk. These results proved that the as‐prepared molecularly imprinted polymers is a potent absorbent for selective recognition of erythromycin, and therefore it may be a promising candidate for practical applications, such as wastewater treatment and detection of erythromycin residues in food.     

基于硅材料的分子印迹聚合物的制备及应用*

分子印迹聚合物因制备简单、稳定性好、且具有分子识别功能使其在色谱分离、固相萃取、化学传感、模拟酶催化等方面有了广泛的应用。近年来,基于硅的分子印迹聚合物发展较为快速。本文主要介绍了以硅为母体材料和以硅为基质材料的分子印迹聚合物的制备及分子识别性质研究,并对其应用进行了分类,在此基础上对其将来的发展进行了展望。     

阴离子印迹聚合物的制备及其应用研究进展

离子印迹聚合物是利用印迹技术对模板离子进行印迹、聚合进而得到能够选择性吸附该离子的一种特殊聚合物.目前的报道大多是阳离子印迹聚合物,因为阴离子模板结构更复杂多样且电荷尺寸比更小,致使阴离子印迹聚合物的发展相对滞后.为能更有效地指导阴离子印迹聚合物的制备,本文概述了阴离子印迹聚合物的发展现状,介绍了与不同阴离子有相互作用...     

分子印迹固相萃取技术在天然产物有效成分分离分析中的应用进展

天然产物体系复杂,尤其是一些活性成分含量较低,采用一般的方法对其进行分离富集难度较大。分子印迹聚合物具有良好的亲和性和专一的选择性,将分子印迹固相萃取技术应用于天然药物资源样品前处理过程,能够选择性地分离富集复杂基质中的目标成分。本文对近几年分子印迹固相萃取技术在天然产物有效成分分离分析中的应用进行了总结,分析物包括黄酮类、多元酚类、生物碱类、有机酸类、苯丙素类、萜类以及其他一些类型的生物活性成分。     

RECENT ADVANCES IN THE PREPARATION OF MOLECULARLY IMPRINTED POLYMERS VIA CONTROLLED RADICAL POLYMERIZATION TECHNIQUES

Molecular imprinting technique is a simple and efficient method for the preparation of polymer materials （i. e., molecularly imprinted polymers, MIPs） with tailor-made recognition sites for certain target molecules. The resulting MIPs have proven to be versatile synthetic receptors due to their high specific recognition ability, favorable mechanical, thermal and chemical stability, and ease of preparation. Recent years have witnessed significant progress in the synthesis and applications of MIPs. This review focus on the recent developments and advances in the preparation of MIPs via various controlled radical polymerization techniques.     

胆固醇分子印迹聚合物的制备及其选择性吸附

随着人们生活水平的逐步提高,因人体内胆固醇过高所产生的疾病呈逐年增加的趋势.近年来的研究表明,胆固醇分子印迹聚合物对胆固醇具有良好的选择性吸附能力.将胆固醇分子印迹聚合物作为胆固醇的识别剂,提取食品中的胆固醇和治疔胆固醇有关的疾病,展现出了良好的应用前景.本文分别从胆固醇分子印迹聚合物的制备方法、识别机理、提高选择性识别途径以及新的印迹方法等方面进行了综述.     

纳米结构分子印迹聚合物及其在药物分析中的应用进展

纳米材料是纳米技术发展的重要基础,它具有许多传统材料所不具备的独特的理化性质,因此有着广泛的应用前景.分子印迹技术是一种通过模拟抗体-抗原相互作用原理,制备具有分子识别功能的聚合物的技术.以纳米材料制备的分子印迹聚合物具有较高的结合容量,较大的选择性和较快的结合动力学特性,近年来备受关注.本文简单概述了零维、一维、二维纳米结构分子印迹聚合物的合成、表征方法及研究现状,并对其在手性药物分析、临床药物分析、传感器及药物残留检测中的应用进行了综述.     

Synthesis of stationary phases that provide group recognition for polychlorinated biphenyls by porogenic fragment template imprinting

Molecular recognition based on imprinted polymers results from the polymerization of functional monomers and cross‐linkers in the presence of a target analyte (i.e. template), with subsequent removal of the template to create synthetic binding sites. However, complete removal of the template is difficult to achieve, thereby leading to template leaching, which adversely affects real‐world analytical applications. To overcome this challenge, the present study utilizes porogenic fragment template imprinting techniques to provide an alternative synthetic strategy to generate molecularly imprinted polymers with molecular recognition toward polychlorinated biphenyls. Thereafter, thus‐generated imprinted polymers have been applied as stationary phases in molecularly imprinted solid‐phase extraction for preconcentrating six “indicator polychlorinated biphenyls” in both organic and aqueous media. Recoveries of up to 98.9% (imprinted polymers) versus 73.0% (conventional C₁₈) in an organic phase, and up to 97.4% (imprinted polymers) versus 89.4% (C₁₈) in an aqueous phase have been achieved corroborating the utility of this advanced sorbent material. Finally, porogenic fragment template imprinting strategies have yielded molecularly imprinted polymers that are useful for the quantitative determination of polychlorinated biphenyls in environmental matrices, which provides a low‐cost strategy for tailoring stationary phases that avoid template leaching in applications in solid‐phase extraction as well as liquid chromatography.     

Molecularly Imprinted Polymers for Stir Bar Sorptive Extraction: Synthesis,Characterization, and Application

Stir bar sorptive extraction is widely used for the preconcentration of organic and inorganic compounds due to its simplicity and versatility. However, commercially available devices are based on nonselective sorbents. Molecularly imprinted polymers provide selective recognition abilities from the template employed during their preparation. In this review, strategies employed for recent for molecularly imprinted polymers employed in stir bar sorptive extraction are described. The advantages and disadvantages are described, as well as future trends involving this preconcentration methodology.     

Molecularly Imprinted Electrochemical Sensors

In this review, the applications of molecularly imprinted polymer (MIP) materials in the area of electrochemical sensors have been explored. The designs of the MIPs containing different polymers, their preparation and their immobilization on the transducer surface have been discussed. Further, the employment of various transducers containing the MIPs based on different electrochemical techniques for determining analytes has been assessed. In addition, the general protocols for getting the electrochemical signal based on the binding ability of analyte with the MIPs have been given. The review ends with describing scope and limitations of the above electrochemical based MIP sensors.     

Evaluation of 2-hydroxyethyl methacrylate as comonomer in the preparation of water-compatible molecularly imprinted polymers for triazinic herbicides

In this work, the preparation and evaluation of water-compatible molecularly imprinted polymers for triazines using 2-hydroxyethyl methacrylate and methacrylic acid as comonomers is described. Four sets of molecularly imprinted and non-imprinted polymers for propazine were prepared at varying monomer molar ratios (from 4:0 to 1:3), and evaluated for the recognition of several triazines directly in aqueous media. The evaluation was performed by loading 1 mL of an aqueous solution containing 500 ng of each selected triazine, washing with 500 μL of acetonitrile, and eluting with 500 μL of methanol followed by 2 × 500 μL of a solution of methanol containing 10% of acetic acid. Final determinations were performed by high-performance liquid chromatography-ultraviolet detection. Improvement in molecular recognition of triazines in water was obtained on those molecularly imprinted polymers incorporating 2-hydroxyethyl methacrylate in 3:1 or 2:2 molar ratios, being the former selected as optimum providing recoveries for propazine up to 80%. A molecularly imprinted solid-phase extraction protocol was developed to ensure that triazines-selective recognition takes place inside selective binding sites in pure water media. Finally, the developed method was successfully applied to the determination of the selected triazines in environmental waters providing limits of detection from 0.16 and the 0.5 μg/L concentration range.     

Preparation of molecularly imprinted polymers for strychnine by precipitation polymerization and multistep swelling and polymerization and their application for the selective extraction of strychnine from nux‐vomica extract powder

Monodisperse molecularly imprinted polymers for strychnine were prepared by precipitation polymerization and multistep swelling and polymerization, respectively. In precipitation polymerization, methacrylic acid and divinylbenzene were used as a functional monomer and crosslinker, respectively, while in multistep swelling and polymerization, methacrylic acid and ethylene glycol dimethacrylate were used as a functional monomer and crosslinker, respectively. The retention and molecular recognition properties of the molecularly imprinted polymers prepared by both methods for strychnine were evaluated using a mixture of sodium phosphate buffer and acetonitrile as a mobile phase by liquid chromatography. In addition to shape recognition, ionic and hydrophobic interactions could affect the retention of strychnine in low acetonitrile content. Furthermore, molecularly imprinted polymers prepared by both methods could selectively recognize strychnine among solutes tested. The retention factors and imprinting factors of strychnine on the molecularly imprinted polymer prepared by precipitation polymerization were 220 and 58, respectively, using 20 mM sodium phosphate buffer (pH 6.0)/acetonitrile (50:50, v/v) as a mobile phase, and those on the molecularly imprinted polymer prepared by multistep swelling and polymerization were 73 and 4.5. These results indicate that precipitation polymerization is suitable for the preparation of a molecularly imprinted polymer for strychnine. Furthermore, the molecularly imprinted polymer could be successfully applied for selective extraction of strychnine in nux‐vomica extract powder.     

Molecular imprinting of natural flavonoid antioxidants: application in solid-phase extraction for the sample pretreatment of natural products prior to HPLC analysis

As shown in the past years, SPE based on molecularly imprinted polymers (MIPs) may provide significant enhancement of selectivity in sample preparation and analyte preconcentration. The objective of this work was the fabrication of MIPs for the specific adsorption of rutin and quercetin. The two flavonoids were used as the template molecules for the preparation of MIP phases in a self-assembly (noncovalent) approach. The produced MIPs were validated with regard to the imprinting efficiency as media for LC and SPE. The retention behavior of several flavonoid compounds was studied using as stationary phases imprinted, control nonimprinted polymers, and commercial silica-based materials. MIPs were applied as materials for the selective SPE and preconcentration of the flavonoids from white and red wine, orange juice, and tea. The collected fractions were analyzed by high-pressure LC. MIP-SPE facilitated specific analyte isolation and effective sample clean-up. The results show that molecularly imprinted SPE can be a useful tool for the simple, selective, and cost-effective pretreatment of samples containing natural antioxidants.